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WO2000023481A1 - Technique de polymerisation d'olefines au moyen de systemes catalytiques de ziegler-natta supportes - Google Patents

Technique de polymerisation d'olefines au moyen de systemes catalytiques de ziegler-natta supportes Download PDF

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Publication number
WO2000023481A1
WO2000023481A1 PCT/EP1999/007785 EP9907785W WO0023481A1 WO 2000023481 A1 WO2000023481 A1 WO 2000023481A1 EP 9907785 W EP9907785 W EP 9907785W WO 0023481 A1 WO0023481 A1 WO 0023481A1
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WO
WIPO (PCT)
Prior art keywords
olefin
pvc
compound
based particles
alpha
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/007785
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English (en)
Inventor
Akhlaq Moman
Atieh Abu-Raqabah
Orass Hamed
Raju Raghavan
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Saudi Basic Industries Corp
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Saudi Basic Industries Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saudi Basic Industries Corp filed Critical Saudi Basic Industries Corp
Priority to EP99955853A priority Critical patent/EP1040132B1/fr
Priority to US09/581,358 priority patent/US6448348B1/en
Priority to DE69914303T priority patent/DE69914303T2/de
Priority to JP2000577206A priority patent/JP4865127B2/ja
Publication of WO2000023481A1 publication Critical patent/WO2000023481A1/fr
Anticipated expiration legal-status Critical
Priority to US10/227,075 priority patent/US20030045659A1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts

Definitions

  • the product polyethylene polymer and copolymers have a density of about 0.91 to 0.97, molecular weight of about 500 to 900,000 grams/mole, a very low level of fines, uniform spherical particles, very good thermal stability and excellent optical properties.
  • heterogeneous metallocene-based catalysts intrinsically possess high activity, though the catalyst precursors and, in particular the cocatalysts required for polymerization, such as aluminoxanes or borane compounds, are very expensive and troublesome in use. Further, another limitation that both catalyst systems share is the lengthy method of preparation and relatively high levels of fines generated in the polymers.
  • U.S. Patent 4,173,547 to Graff describes a supported catalyst prepared by treating a support, for example silica, with both an organoaluminum and an organomagnesium compound. The treated support was then contacted with a tetravalent titanium compound.
  • U.S. Patent No. 3,787,384 to Stevens et al. discloses a catalyst prepared by first reacting a silica support with a Grignard reagent and then combining the mixture with a tetravalent titanium compound.
  • the active catalyst components were deposited on the polymeric support by physical impregnation.
  • Other physical impregnation methods include those described in U.S. Pat. No. 4,568,730 to Graves whereby polymer resins of styrene-divinylbenzene are partially softened and the active catalyst components are homogeneously mixed in the resin to form a mass, which was subsequently pelletized or extruded into catalyst particles.
  • the activity of the above- described polymer supported catalysts is not higher than that of metal oxide supported Ziegler-Natta catalysts.
  • Polypropylene and polyethylene have also found use as polymeric supports, where the polymeric material is typically ground with the catalyst components, which represents a difficult and complicated catalyst preparation procedure.
  • the support material there remains a significant concern as to the ability of the support material to retain the active species, deposited by physical impregnation, during polymerization conditions and thus generate, for example, fines.
  • Hsu et al, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 32,2135 (1994) have used poly(ethylene-co-acrylic acid) as a support for Ziegler-Natta catalysts and the catalyst activity was found to be similar to that of the magnesium chloride supported catalyst.
  • This present invention provides a process of making ethylene polymers and ethylene/alpha olefins (C - C 8 ) copolymers in slurry or gas phase, having a wide density range of about 0.91 to 0.97 grams/cm 3 and weight average molecular weight (Mw) of about 500 to 900,000 grams/mole and molecular weight distribution range of 2 to 10.
  • the product ethylene homopolymers and copolymers have a uniform spherical particle morphology, very low level of fines and catalyst residues, improved thermal stability, excellent optical and better environmental stress cracking resistance (ESCR) than products made with other catalysts heretofore known in the art.
  • the ethylene homopolymers and copolymers can be produced with the very highly active new Ziegler-Natta catalyst systems including at least a transition metal compound, a magnesium compound and an aluminum compound, chemically anchored on polymeric particles having labile active sites.
  • olefin and especially polyethylene polymers and copolymers are provided which have a density of from about 0.91 to about 0.97 grams/cm 3 molecular weight of from about 500 to about 900,000 grams/mole, a very low level of fines, uniform spherical particles, very good thermal stability and excellent optical properties. Additionally, by using the process of the present invention copolymers of ethylene with alpha olefins are obtained at a productivity > 1,000,000 gm PE/gm Ti.
  • the ethylene homopolymers and copolymers which may be prepared by the process of the present invention can have a wide density range of from about 0.91 to about 0.97 grams/cm 3 .
  • the process of the present invention provides polyolefins, and preferably high density polyethylene and linear low density polyethylene.
  • the density of the polymer at a given melt index can be regulated by the amount of the alpha olefin (C to C 8 ) comonomer used.
  • the amount of alpha olefin comonomer needed to achieve the same density is varied according to the type of comonomer used.
  • alpha olefins can include propylene, 1-butene, 1-pentene, 4-methyl 1- pentene, 1-hexene, 1-heptene and 1-octene.
  • Mw average molecular weight
  • the average molecular weight (Mw) grams/mole of the polymers obtained in accordance with this invention ranges from 500 to 900,000 grams/mole or higher, preferably from 10,000 to 750,000 grams/mole, depending on the amount of hydrogen used, the polymerization temperature and the polymer density attained.
  • the homopolymers and copolymers of the present invention have a melt index (MI) range of more than 0 and up to 100, preferably between 0.3 to 50.
  • the polydispersities i.e., molecular weight distribution (MWD) of the produced polymers expressed as molecular weight/number average molecular weight of the polymer (Mw/Mn), is in the range of about 2 to 10.
  • MFD molecular weight distribution
  • MFR polymer melt flow ratio
  • the polymers of the present invention have an MFR in the range of about 15 to 60, preferably 20 to 40. Polymers having such a wide range of MFR are capable of being used in molding and film applications.
  • the polymers of the present invention are granular materials, uniform and spherical particles with an average particle size of about 0.1 to 4 mm in diameter, and a very low level of fines.
  • the bulk density of the polymer ranges from 0.20 to 0.35 g/cm 3 .
  • the solid catalyst component (catalyst precursor) used in the present invention contains at least a transition metal compound, a magnesium compound, an aluminum compound and a polymeric material having a mean particle diameter of 5 to 1000 ⁇ m, a pore volume of 0.1 cmVg or above and a pore diameter of from 20 to 10,000 Angstrom, preferably from 50 ⁇ A to 10,000A and a surface area of from 0.1 m 2 /gm to 100 m 2 /gm, preferably from 0.2 m 2 /gm to 15 m 2 /gm.
  • the transition metal compound used for the synthesis of the solid catalyst component in the invention is represented by the general formula M(OR 1 ) n X -n, wherein M represents a transition metal of Group IV A, VA, VIA, VIIA or VIII of the Periodic Table of the Elements, R 1 represents a alkyl group having 1 to 20 carbon atoms, X represents a halogen atom and n represents a number satisfying 0 ⁇ n ⁇ 4.
  • Nonlimiting examples of the transition metal are titanium, vanadium, or zirconium.
  • R 1 include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl and the like.
  • transition metal compounds include the following: titanium tetrachloride, methoxy titanium trichloride, dimethoxy titanium dichloride, ethoxy titanium trichloride, diethoxy titanium dichloride, propoxy titanium trichloride, dipropoxy titanium dichloride, butoxy titanium trichloride, butoxy titanium dichloride, vanadium trichloride, vanadium tetrachloride, vanadium oxytrichloride, and zirconium tetrachloride.
  • the magnesium compound used for the catalyst synthesis in the invention include Grignard compounds represented by the general formula R 2 MgX, wherein R 2 is an alkyl group of 1 to 20 carbon atoms and X is a halogen atom.
  • Other preferred magnesium compounds are represented by the general formula R R Mg, wherein R 3 and R 4 are each an alkyl group of 1 to 20 carbon atoms.
  • Preferred examples of the above mentioned magnesium compounds include the following: diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dihexylmagnesium, butyloctylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride and the like.
  • magnesium compounds described above may also be used in catalyst preparation as a mixture with an organoaluminum compound.
  • organoaluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum and the like; and alkylalumoxanes such as methylalumoxane, ethylalumoxane and the like.
  • the mixture of the magnesium compound and the organoaluminum compound in this invention can be used with a Mg: Al molar ratio of 99:1 to 50:50, and preferably 98:2 to 80:20 and more preferably 96:4 to 85:15.
  • the polymer particles used as supports in the present invention are in the form of distinct spherical particles, on which the active catalyst component is chemically bonded, wherein the ratio of active catalyst component to polymeric support is less than 3% by weight, preferably less than 1% by weight, more preferably less than 0.7% by weight.
  • catalysts prepared in the prior art using polymeric materials relied on physical impregnation of the catalyst active sites on the polymeric materials.
  • the polymer particles used in the present invention have a spherical shape with a particle diameter of 5 to 800 ⁇ m, preferably 10 to 600 ⁇ m, and more preferably 15 to 500 ⁇ m, a pore diameter of 20 to 10,000 Angstroms, preferably from 50 ⁇ A to 10,000A, surface area of from 0.1 m 2 /gm to 100 m 2 /gm, preferably from 0.2 m 2 /gm to 15 m /gm and a pore volume of 0.1 cm /g or above, preferably 0.2 cm /g or above. Uniformity of particle size is not critical and in fact catalyst supports having nonuniform particle sizes are preferred.
  • a catalyst support having a median particle size of 65 microns it is preferred that at least 10% of the support particles have a diameter of greater than 85 microns, and at least 10% of the support particles have a diameter of less than 45 microns.
  • the polymeric supports used in the catalyst preparation of the present invention include polymer beads made of thermoplastic polymers. Polymer supports made of polyvinylchloride are preferred, and non-cross linked polyvinylchloride particles are most preferred.
  • the polymer particles used in the present invention have surface active sites such as labile chlorine atoms.
  • these active sites are reacted stoichiometrically with the organometallic compound, namely a magnesium containing compound and/or an aluminum containing compound.
  • the use of the polymer particles mentioned in the catalyst preparation of the invention offers significant advantages over traditional olefin polymerization catalysts using supports such as silica or magnesium chloride.
  • the polymer particles described in catalyst preparation of the invention require no high temperature and prolonged dehydration steps prior to their use in catalyst synthesis, thereby simplifying the synthesis process and thus reducing the overall cost of catalyst preparation.
  • the cost of the polymeric support used in the present invention is substantially cheaper than silica or magnesium chloride supports.
  • the catalyst in the present invention uses significantly lower levels of catalyst components for catalyst precursor preparation than silica or magnesium chloride supported catalysts. Also, the catalyst in the present invention is more active than conventional silica or magnesium supported Ziegler-Natta catalysts and supported metallocene catalysts. It has been unexpectedly found that the catalyst compositions of the present invention have an activity of more than 60,000g polyethylene per mmol of titanium per 100 psi per hour, thereby providing polymers of superior clarity.
  • polyvinylchloride is used in the synthesis of the solid catalyst component.
  • the synthesis of the solid catalyst component in the present invention involves introducing the polymeric material described above into a vessel and adding a diluent. Suitable diluents include isopentane, hexane, cyclohexane, heptane, isooctane and pentamethylheptane.
  • the polymeric material is treated with either a magnesium compound described above or a mix of a magnesium compound and aluminum compound of the type described above at a temperature in the range of 20°C to 150°C, preferably 50°C to 110°C.
  • the ratio of organometallic compound to the polymer support can be in the range of 0.05 mmol to 20 mmol per gram polymer, preferably 0.1 mmol to 10 mmol per gram polymer, and more preferably 0.2 mmol to 2 mmol per gram polymer.
  • the magnesium or magnesium-aluminum modified polymeric material is then treated with a transition metal compound of the type described above at a temperature in the range of 20°C to 150°C, preferably 50°C to 110°C.
  • a transition metal compound of the type described above preferably 50°C to 110°C.
  • TiCl 4 , TiCl 3 , Ti (OC 2 H 5 ) 3 Cl, VC1 4 , VOCl 3 , ZrCl 4 , ZrCl 3 (OC 2 H 5 ) are preferred transition metal conpounds, TiCl 4 , and ZrCl 4 are more preferred.
  • the produced solid catalyst component is washed with a suitable solvent such isopentane, hexane, cyclohexane, heptane, isooctane and pentamethylheptane, preferably isopentane or hexane.
  • a suitable solvent such isopentane, hexane, cyclohexane, heptane, isooctane and pentamethylheptane, preferably isopentane or hexane.
  • the solid catalyst component is dried using a nitrogen purge at a temperature in the range of 20°C to 100°C, preferably 30°C to 80°C.
  • the free-flowing solid particulate catalyst is activated with suitable activators, also known as cocatalysts or catalyst promoters.
  • suitable activators also known as cocatalysts or catalyst promoters.
  • the activation process can be a one step in which the catalyst is fully activated in the reactor, or two steps, in which the catalyst is partially activated outside the reactor and the complete activation occurs inside the reactor.
  • the preferred compounds for activation of the solid catalyst component are organoaluminum compounds.
  • organoaluminum compounds which can be used as activators in the present invention along with the solid catalyst component are represented by the general formulas R 5 nAlX 3-n or
  • organoaluminum compounds include triethylaluminum (TEAL), triisobutylaluminum (TIBA), tri n- hexylaluminum (TnHAL), diethylaluminum chloride, methylalumoxane, ethylalumoxane, and mixtures thereof.
  • the organoaluminum compound in this invention can be used in the range of from 1 to 1500 moles per one mole of transition metal in the said catalyst, and more preferably in the range of 10 to 800 moles per one mole of transition metal.
  • the olefin polymerization may be conducted in solution, slurry or gas phase process, generally, at a temperature range of about 30°C to 110°C, preferably 50°C to 95°C, and at a pressure in the range of about 5 to 40 bars, more preferably 15 to 30 bar.
  • ethylene copolymers with C -C 8 alpha-olefins are readily prepared by the present invention.
  • Particular examples include ethylene/propylene, ethylene/ 1-hexene, ethylene/ 1-butene and ethylene/ 1-octene.
  • the molecular weight of the polymer can be effectively controlled by varying process conditions such as the hydrogen pressure used, as evidenced by the change in the melt index of the polymer produced.
  • the catalyst compositions of the present invention are useful for olefin polymerization in the absence of electron donor compounds which are sometimes utilized to control the stereo selectivity of the catalyst during polymerization.
  • MI Melt Index
  • MFI Melt Flow Index
  • MFR Melt Flow Ratio
  • a crystal of iodine was added, followed by 255 cm 3 of dibutylether.
  • 53.0 cm 3 of butylchloride was gradually added to the flask over a period of 45 minutes, while stirring and maintaining the temperature at 105°C.
  • the resulting mixture in the flask was stirred for 90 minutes after the completion of butylchloride addition at 105°C.
  • 400 cm 3 of n-heptane was added and stirring was carried out for a further period of 90 minutes at 105°C.
  • the reaction mixture was cooled to room temperature, and the solid matter was filtered off.
  • the modified polyvinylchloride was slurried using 30 cm 3 of heptane, and stirred with 10 cm 3 of a one molar titanium tetrachloride solution in heptane at 70°C for 60 minutes.
  • the supernatant liquid was decanted and the resulting solid product was washed by stirring with 100 cm 3 of heptane and then the heptane was removed, then the solid product was washed again with 100 cm 3 of isopentane, and then washed three more times with 75 cm 3 of isopentane.
  • the solid catalyst was dried using a nitrogen purge for thirty minutes to yield a free-flowing brown colored solid product.
  • the solid catalyst component was analyzed by atomic adsorption spectroscopy and was found to contain 0.2% by weight of titanium atoms, 1.0% by weight of magnesium atoms and 0.05% by weight of aluminum atoms.
  • the modified polyvinylchloride was slurried using 30 cm 3 of heptane, and stirred with 5 cm 3 of a one molar titanium tetrachloride solution in heptane at 70°C for 30 minutes.
  • the supernatant liquid was decanted and the resulting solid product was washed by stirring with 100 cm 3 of heptane and then the heptane was removed, then the solid product was washed again with 100 cm 3 of isopentane, and then washed three times with 75 cm 3 of isopentane.
  • the solid catalyst was dried using a nitrogen purge for thirty minutes to yield a free-flowing brown colored solid product.
  • the solid catalyst component was found to contain 0.27% by weight of titanium atoms and 0.52% by weight of magnesium atoms.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Ce procédé de polymérisation catalytique aux fins de la préparation de produits polymères consiste, soit en une homopolymérisation d'oléfines, soitn une copolymérisation d'oléfines à l'aide d'oléfines-α. Cette polymérisation se fait en présence d'un précurseur catalytique solide et d'un cocatalyseur. Le précurseur catalytique comporte un métal de transition, un composé magnésien, un composé d'aluminium et des particules polymères.
PCT/EP1999/007785 1998-10-16 1999-10-13 Technique de polymerisation d'olefines au moyen de systemes catalytiques de ziegler-natta supportes Ceased WO2000023481A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP99955853A EP1040132B1 (fr) 1998-10-16 1999-10-13 Technique de polymerisation d'olefines au moyen de systemes catalytiques de ziegler-natta supportes
US09/581,358 US6448348B1 (en) 1998-10-16 1999-10-13 Process for polymerizing olefins with supported Ziegler-Natta catalyst systems
DE69914303T DE69914303T2 (de) 1998-10-16 1999-10-13 Verfahren zur polymerisation von olefinen mit geträgerten ziegler-natta katalysatorsystemen
JP2000577206A JP4865127B2 (ja) 1998-10-16 1999-10-13 坦持チーグラー−ナッタ触媒系によるオレフィンの重合方法
US10/227,075 US20030045659A1 (en) 1998-10-16 2002-08-23 Process for polymerizing olefins with supported Ziegler-Natta catalyst systems

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10466998P 1998-10-16 1998-10-16
US60/104,669 1998-10-16
US11099598P 1998-12-04 1998-12-04
US60/110,995 1998-12-04

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US (1) US6448348B1 (fr)
EP (1) EP1040132B1 (fr)
JP (1) JP4865127B2 (fr)
DE (1) DE69914303T2 (fr)
WO (1) WO2000023481A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1233029A1 (fr) * 2001-02-15 2002-08-21 Saudi Basic Industries Corporation Composition de catalyseur sur support pour la polymerisation d'olefines; methode pour sa preparation et procede de polymerisation utilisant ladite
WO2013133956A3 (fr) * 2012-03-05 2013-12-19 Univation Technologies, Llc Procédés de production de compositions de catalyseur et produits polymères produits à partir de celles-ci

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Publication number Priority date Publication date Assignee Title
EP1231223B1 (fr) * 2001-02-07 2004-04-28 Saudi Basic Industries Corporation Procédé de polymérisation d'oléfines
ES2240613T3 (es) * 2002-07-12 2005-10-16 Saudi Basic Industries Corporation Composicion catalizadora ziegler-metaloceno soportada y procedimiento de polimerizacion y copolimerizacion de olefinas con alfa-olefinas usando sistemas catalizadores novedosos.
CN100447167C (zh) * 2006-06-30 2008-12-31 吉林市朋力科技开发有限公司 烯烃聚合用聚合物载体齐格勒-纳塔催化剂及制备方法
FR2909989A1 (fr) * 2006-12-18 2008-06-20 Arkema France Procede de preparation de nanotubes de carbone a partir d'une source de carbone integree au catalyseur

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WO1997048742A1 (fr) * 1996-06-21 1997-12-24 W. R. Grace & Co.-Conn. Supports d'agregats portant des catalyseurs de polymerisation d'olefines

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FR1529845A (fr) * 1967-05-10 1968-06-21 Solvay Perfectionnements apportés à la polymérisation d'oléfines
US4940682A (en) * 1987-10-28 1990-07-10 Sumitomo Chemical Company, Limited Solid catalyst component for olefin polymerization
WO1997048742A1 (fr) * 1996-06-21 1997-12-24 W. R. Grace & Co.-Conn. Supports d'agregats portant des catalyseurs de polymerisation d'olefines

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1233029A1 (fr) * 2001-02-15 2002-08-21 Saudi Basic Industries Corporation Composition de catalyseur sur support pour la polymerisation d'olefines; methode pour sa preparation et procede de polymerisation utilisant ladite
WO2002085958A3 (fr) * 2001-02-15 2002-12-12 Saudi Basic Ind Corp Composition catalytique soutenue pour polymerisation d'olefines, procede permettant de la preparer et processus de polymerisation utilisant ladite composition
US7060646B2 (en) 2001-02-15 2006-06-13 Saudi Basic Industries Corporation Supported catalyst composition for polymerization of olefins, method for preparing the same and process for polymerization using the same
WO2013133956A3 (fr) * 2012-03-05 2013-12-19 Univation Technologies, Llc Procédés de production de compositions de catalyseur et produits polymères produits à partir de celles-ci
US9487601B2 (en) 2012-03-05 2016-11-08 Univation Technologies, Llc Methods for making catalyst compositions and polymer products produced therefrom
RU2640048C2 (ru) * 2012-03-05 2017-12-26 Юнивейшн Текнолоджиз, Ллк Способ получения каталитических композиций и полимерных продуктов, полученных с применением этих каталитических композиций
US9975974B2 (en) 2012-03-05 2018-05-22 Univation Technologies, Llc Methods for making catalyst compositions and polymer products produced therefrom

Also Published As

Publication number Publication date
EP1040132B1 (fr) 2004-01-21
US6448348B1 (en) 2002-09-10
JP4865127B2 (ja) 2012-02-01
DE69914303T2 (de) 2004-11-25
JP2002527585A (ja) 2002-08-27
EP1040132A1 (fr) 2000-10-04
DE69914303D1 (de) 2004-02-26

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